DE10151922B4 - Biotechnical production of an oil binder from leather-containing raw materials - Google Patents

Abstract

method for producing an oil binder made of leather-containing materials, characterized in that the leather-containing material by means of suitable crushers converted into granular form, with oil-degrading microorganisms and then sealed by enzymatic reaction and is hydrophobicized.

Description

object This invention is the preparation of a base oil binder of leather-containing raw materials and its use in the field of Decontamination of oil-contaminated solid surfaces and liquids. In doing so, the surface becomes of the leather sealed by enzymatic reactions and simultaneously hydrophobic.

sorbents are used in various industries in large quantities for absorbing spilled oil on floors used. Fire brigades and water guards put on oil binders at oil spills Land and water. Oil binder, which can be used universally on water and land and at the same time one have high oil binding capacity, are currently not commercially available.

own Experiments showed that leather-containing materials in granular form over a high oil absorption capacity and a good buoyancy feature. A use on waters is currently due, however, to the leakage of organic matter the oil binder in the water body not possible. However, it could be proved that the leather surface by the use of certain enzymes can be modified in the way that crosslinking occurs at the surface of the granule particles and so the leakage of organic matter is minimized.

Preferably come here enzymes from the group of phenol oxidases such as polyphenol oxidases, Laccases, tyrosinases used that are capable of aromatic amino acids from the collage framework of the leather to oxidize while a radical polymerization to initiate, which also leads to a copolymerization of others Amino compounds leads. In this way, a kind of sealing of the surface of the Granules achieved, both the leakage of organic compounds from the granules as well as the abrasion of the smallest leather particles significantly reduced. The legal requirements for oil binders for the Use on waters are thus achieved.

• – ein- oder mehrwertige Phenole (z. B. Brenzkatechin, Pyrogallol und deren Derivate)
• – Ligninabbauprodukte (z.B. Kaffeesäure, Hydrochinon)
• – ligninartige Abfallstoffe (z.B. Sulfitablauge, Sulfatlignin)
• – Abfallstoffe aus der Holzrindenverwertung
• – Proteine oder proteinhaltige Abfallstoffe (z.B. Casein, Caseinpepton, Gelatine, Molke)
• – Tannine und andere Gerbstoffe.

The enzymatic reaction can be improved if phenolic compounds, aromatic amino acids or waste containing these substances are added to the reaction mixture in small amounts. These substances can be

• Mono- or polyhydric phenols (eg pyrocatechol, pyrogallol and their derivatives)
• Lignin degradation products (eg caffeic acid, hydroquinone)
• Ligninous wastes (eg sulphite waste liquor, sulphate lignin)
• - Waste from wood bark recycling
• Proteins or protein-containing wastes (eg casein, casein peptone, gelatin, whey)
• - tannins and other tannins.

Except the Use of phenol oxidases networking of the leather surface also by the addition of Achieve peroxidases and transglutaminases.

With the increase the degree of crosslinking on the leather surface is simultaneously a Increase in hydrophobicity achieved, so that the oil binding capacity improves becomes.

When Raw material for the manufacturing process can Natural leather, various types of tanned leather, leather waste and leathery waste such as. Old shoes are used.

• 1. Vorzerkleinerung des Ledernmaterials mit einem Schredder auf eine Korngröße < 4 cm
• 2. Entfernung der Metalle
• 3. Granulierung des Ledernmaterials mit einer Schneidmühle auf eine Korngröße < 5 mm
• 4. Zugabe von ölabbauenden Mikroorganismen
• 5. Enzymatische Versiegelung.

The manufacturing process for the oil binder consists of

• 1. Pre-shredding the leather material with a shredder to a grain size <4 cm
• 2. Removal of the metals
• 3. Granulation of the leather material with a granulator to a particle size <5 mm
• 4. Addition of oil-degrading microorganisms
• 5. Enzymatic sealing.

Prior art, advantages of the procedure

Either own experiments as well as different publications show that Leather very good for removing hydrocarbons from both solid as well as liquid surfaces is suitable [1,2].

Unfortunately However, for the use on waters the legal requirements regarding the exit of organic Dry substance (OTS) into the water (Limit: <20 mg / l, test method according to [3]) not reached. Even after repeated washing of the leather granules with water these values are over 100 mg / l [4]. Thus, one of ASA Spezialenzyme GmbH at the Materialprüfungsamt Nordrhein-Westfalen, Dortmund, applied for authorization of leather granules as an oil binder for the Use on waters not granted.

The enzymatic action of phenol oxidases and peroxidases arises today as follows: mono- and polyhydric phenols, their derivatives (Halogen, amino, nitro compounds) and aromatic amino acids (tyrosine) are oxidized in the presence of oxygen (peroxidases: hydrogen peroxide). This forms radicals that cause polymerization of the reaction products to humic substance-like, dark brown colored Cause polymers [5].

Also lignin degradation products, ligninous wastes, wood cattle waste, Proteins and tannins or components of these materials can be reacted by phenol oxidases and / or incorporated into the polymers. Thus, phenol oxidases and lignin sulfonate were used to develop a bonding agent for the bonding of chipboard [6].

transglutaminases catalyze cross-linking of protein molecules by linking Glutamate and lysine residues within the molecule, creating gel-like structures arise. The enzyme is already used in the food industry [7].

• – die Oberfläche der Granulatteilchen wird durch die Quervernetzung der Peptidketten des Collagengerüstes versiegelt und gleichzeitig hydrophobiert.
• – Der Austritt von organischer Substanz sowie der Abrieb von Lederkleinstteilchen wird minimiert und somit der gesetzliche Grenzwert zum Einsatz auf Gewässern unterschritten.
• – Die Schwimmfähigkeit des Ledergranulates auf Wasser wird verbessert.
• – Die Ölhaltefähigkeit wird erhöht.
• – Die Ölbindungskapazität wird leicht erhöht.

The treatment of leather granules with the described enzymes and optionally with the addition of phenolic compounds, aromatic amino acids or waste materials achieves the following effects:

• - The surface of the granules is sealed by the crosslinking of the peptide chains of the collagen scaffold and hydrophobic at the same time.
• - The leakage of organic matter and the abrasion of leather small particles is minimized and thus falls below the legal limit for use in waters.
• - The buoyancy of the leather granules on water is improved.
• - The oil holding capacity is increased.
• - The oil binding capacity is slightly increased.

Example 1: Preparation an oil binder made of old leather

500 kg of used leather is shredded (Alpine company, sieve size 3 cm) pre-shredded and over conveyor belt transported on the over a magnetic separator metals are removed. After that it will be Material in a granulator (Rapid) crushed to a particle size <5 mm.

Over a sprayer becomes afterwards a watery Suspension with oil-degrading Bacteria applied to the material. About another spraying device is a mixture of 20 units of laccase and 2 g of casein per kg Leather applied to the material.

Example 2: Use of the oil binder for removing oils from the water surface

One Water basin is filled with 50 liters of tap water and 1 liter of waste oil added until an oil spill forms. Thereafter, 100 g of oil binder on the oil carpet sprinkled. Based on the oil streaks is to watch that the oil selectively from the oil binder is sucked up. The process takes 10 minutes. After that it will be Skimmed oil binder skimmed off. It there is no visible oil on the water surface back.

Example 3: Use of the oil binder for removing oils of solid surfaces

On 1 liter of used oil is poured out of an asphalt surface. Thereafter, 200 g of oil binder on the oil carpet sprinkled. After 30 minutes, the laden oil is swept up with a broom. There is no visible oil back on the floor. The surface is not smooth anymore.

literature

• 1. DE 2810140 A1 (1978)
• Second DE 19849427 A1 (2000)
• 3. "Requirements to Ölbinder ", Joint Ministerialblatt G3191 A; Federal Minister for Environment, Nature Conservation and Nuclear Safety (1998)
• 4. ASA Spezialenzyme GmbH, own experiments
• 5. Haider, K .; Arch. Microbiol. 64, (1969) 338-348
• 6th DE 3644397 C1 (1988)
• 7. Motoki, M. et al .; Agric. Biol. Chem., 50, (1986) 3025-3030

Claims (17)

Process for the preparation of an oil binder of leather-containing materials, characterized in that the leather-containing material is converted by means of suitable crushing machines in granular form, mixed with oil-degrading microorganisms and then sealed by enzymatic reaction and hydrophobicized. Method according to claim 1, characterized in that that the reaction mixture to carry out the enzymatic reaction Contains granules of leathery material, enzymes and water. Method according to at least one of the preceding Claims, characterized in that under leather-containing material in particular untreated leather of all kinds, tanned in different ways Leather, old leather, chrome shavings, Old shoes, artificial leather and all other materials, the leather contained, is to be understood. Method according to at least one of the preceding Claims, characterized in that the reaction mixture for carrying out the enzymatic Reaction enzymes from the groups phenol oxidases, peroxidases and Contains transglutaminases. Method according to at least one of the preceding Claims, characterized in that the enzymes used are microbial, of plant or animal origin. Method according to at least one of the preceding Claims, characterized in that among phenol oxidases all kinds of Enzymes which are present in the presence of oxygen and oxidize polyhydric phenols and their derivatives. Method according to at least one of the preceding Claims, characterized in that from the group of phenol oxidases the Enzymes laccase, polyphenol oxidase and tyrosinase are used. Method according to at least one of the preceding Claims, characterized in that among peroxidases all kinds of enzymes which are understood in the presence of hydrogen peroxide and polyhydric phenols, their derivatives, lignin and lignin degradation products oxidize. Method according to at least one of the preceding Claims, characterized in that from the group of peroxidases the Enzymes horseradish peroxidase, lignin peroxidase, chloroperoxidase and manganese peroxidase can be used. Method according to at least one of the preceding Claims, characterized in that the reaction mixture for carrying out the enzymatic Reaction mono- or polyhydric phenols, their derivatives, lignin degradation products, ligninous waste, wood cattle waste, Proteins, protein-containing wastes, tannins and other tannins be added. Method according to at least one of the preceding Claims, characterized in that the reaction mixture for carrying out the enzymatic In particular, one or more of the following compounds to be added: caffeic acid, Hydroquinone, pyrocatechol, pyrogallol, guaiacol, 2,6-dimethoxyphenol, 3-methylcatechol, 4-methylcatechol, sulphite liquor, sulphate lignin, lignosulfonic Casein, casein peptone, gelatin, whey. Method according to at least one of the preceding Claims, characterized in that the reaction mixture for carrying out the Enzymatic reaction added transglutaminase microbial Origin is. Method according to claim 12, characterized in that that the reaction mixture to carry out the enzymatic reaction Lysine and glutamic acid be added. Process according to claims 1 to 13, characterized that contained in the oil binder Microorganisms are capable of adsorbed to the oil binder oils and waste oils of various kinds Biodegrade kind. Use of according to at least one of claims 1 to 13 prepared oil binder for removing oils of watery Liquids, characterized in that the oil binder mineral oils, petroleum, gear oils, engine oils, hydraulic oils, rapeseed oil and waste oils of various, Species selectively adsorbed and these oils from aqueous liquids, in particular of the water surface-removed become. Use of according to at least one of claims 1 to 13 prepared oil binder for removing oils of solid surfaces characterized in that with the oil binder mineral oils, petroleum, gear oils, engine oils, hydraulic oils, rapeseed oil and waste oils various Kind of solid surfaces be removed. Process for the further processing of the oil binder, characterized in that the laden with oils and waste oils of various kinds oil binder mixed and aerated in a suitable reactor with nutrient solution, about the oil degradation to accelerate.